Water soluble photochromic compounds, compositions and optical elements comprising the compounds

ABSTRACT

Described are novel water soluble photochromic naphthopyran and benzopyran compounds having an alkylaminoalkylamino group on the naphtho- or benzo-portions and/or pyran portions thereof. These compounds may be represented by one of the following graphic formulae: ##STR1## wherein R 1  is an alkylaminoalkylamino group. Articles such as ophthalmic lenses or other plastic transparencies and coating compositions such as paints and inks that incorporate the novel water soluble compounds are also described.

DESCRIPTION OF THE INVENTION

The present invention relates to certain novel naphthopyran andbenzopyran compounds. More particularly, this invention relates to novelphotochromic water soluble naphthopyran and benzopyran compounds and tocompositions and articles containing such novel water soluble compounds.When exposed to electromagnetic radiation containing ultraviolet rays,such as the ultraviolet radiation in sunlight or the light of a mercurylamp, many photochromic compounds exhibit a reversible change in color.When the ultraviolet radiation is discontinued, such a photochromiccompound will return to its original color or colorless state.

Various classes of photochromic compounds have been synthesized andsuggested for use in applications in which a sunlight-induced reversiblecolor change or darkening is desired. U.S. Pat. No. 3,567,605 (Becker)describes a series of pyran derivatives, including certain benzopyransand naphthopyrans. These compounds are described as derivatives ofchromene and are reported to undergo a color change, e.g., fromcolorless to yellow-orange, on irradiation by ultraviolet light attemperatures below about -30° C. Irradiation of the compounds withvisible light or upon raising the temperature to above about 0° C. isreported to reverse the coloration to a colorless state.

U.S. Pat. No. 5,458,814 describes photochromic2,2-disubstituted-5,6-substituted-2H-naphtho 1,2-b!pyran compositionsprimarily for use in lenses and other plastic transparencies having anacceptable fade rate in addition to a high activated intensity and ahigh coloration rate. U.S. Pat. No. 5,466,398 discloses3,3-disubstituted-8-substituted-3H-naphtho 2,1-b!pyran compositions forsimilar uses having additional substituents at the number 7 or number 9carbon atom of the naphthopyran and which exhibit an improved solarresponse and higher activating wavelength than unsubstitutednaphthopyrans.

U.S. Pat. No. 5,289,547 describes a method for authenticating articleswherein a photochromic compound is incorporated into ink which isprinted or coated onto an article. The photochromic compound isdissolved in the ink in sufficient quantities to produce a visibledisplay of a predetermined pattern or the like when the ink isilluminated by appropriate wavelengths of light.

The compounds disclosed in each of these patents are not water soluble,thus preparations thereof require is organic solvents. Many suitableorganic solvents are hazardous materials requiring specialized handlingand disposal procedures.

United Kingdom Patent Application GB 2209751A discloses a method ofproducing water soluble photochromic fulgides, fulgimides andadamantylidene spiropyrans by incorporating therein a sulphonic acid orchlorosulphonic acid group or acid salt. The photochromic compounds aresulphonated by treatment with sulphur trioxide or a dioxan-sulfurtrioxide to impart water solubility thereto.

The present invention relates to novel water soluble photochromiccompounds namely, certain 2H-naphtho 1,2-b!pyrans, 3H-naphtho2,1-b!pyrans and benzopyrans each having at least onealkylaminoalkylamino group thereon. In an acidic environment, thealkylaminoalkylamino groups form quaternary salts, thereby rendering thephotochromic compounds water soluble. These compounds have certainsubstituents on the pyran ring at the position ortho to the oxygen atom.Certain substituents are also present on the 2H-naphtho 1,2-b!pyrancompounds at the number 5 and 6 carbon atoms of the naphtho portion ofthe naphthopyran, on the 3H-naphtho 2,1-b!pyran compounds at the number8 and 9 carbon atoms of the naphtho portion of the naphthopyran and onthe benzopyran compounds at the 5 and 6 carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION

In recent years, photochromic plastic materials, particularly plasticmaterials for optical applications, have been the subject ofconsiderable attention. In particular, photochromic ophthalmic plasticlenses have been investigated because of the weight advantage theyoffer, vis-a-vis, glass lenses. Moreover, photochromic transparenciesfor vehicles, such as cars and airplanes, have been of interest becauseof the potential safety features that such transparencies offer.

Photochromic compounds are also useful in various non-ophthalmicarticles such as inks, paints and coatings for security documents anddecorative or fashion items. In particular, water soluble photochromiccompounds possess processing and handling features not present inconventional water insoluble photochromic compounds.

In accordance with the present invention, it has been discovered thatcertain photochromic 2H-naphtho 1,2-b!pyrans, 3H-naphtho 2,1-b!pyransand benzopyrans which are traditionally water insoluble may now be madewater soluble by including thereon an alkylaminoalkylamino group. Whenacidified, the alkylaminoalkylamino group(s) forms quaternary ammoniumsalts rendering the compounds water soluble. These compounds may bedescribed as 2H-naphtho 1,2-b!pyrans and 3H-naphtho 2,1-b!pyrans, eachhaving certain substituents at the 2 position and the 3 position,respectively, of the pyran ring and an alkylaminoalkylamino group on thenaphtho portion of the naphthopyran ring. The 2H-naphtho 1,2-b!pyransand the 3H-naphtho 2,1-b!pyrans also have certain other substituents atthe 5 position and the 9 position, respectively, on the naphtho portionof the naphthopyran ring. The compounds of the present invention alsoinclude benzopyrans having the same certain substituents at the 2position of the pyran ring, certain other substituents at the 5 carbonatom and an alkylaminoalkylamino group at the 6 carbon atom of thebenzopyran ring. The aforedescribed naphthopyrans and benzopyrans may berepresented by the following graphic formulae I, II and III in which thenumbers 1 through 10 in graphic formulae I and II identify the ringatoms of the naphthopyrans and the numbers 1 through 8 in the graphicformula III identify the ring atoms of the benzopyran. In the definitionof the substituents shown in graphic formulae I, II and III, likesymbols have the same meaning unless stated otherwise. ##STR2## Ingraphic formulae I, II and III, R₁ is an alkylaminoalkylamino grouprepresented by graphic formula IV: ##STR3## wherein R₄ is C₁ -C₃ alkyl,phenyl(C₁ -C₃)alkyl, phenyl or R₅, A is an anion, e.g., chloride,bromide, sulfate and phosphate.

In graphic formula IV, R₅ is a group represented by graphic formula V.##STR4## wherein R₆ and R₇ are each C₁ -C₃ alkyl or C₁ -C₃ alkylamino(C₁-C₃)alkylamino and m is the integer 2, 3 or 4. Preferably, R₄ is methylor 3-dimethylaminopropyl, and R₆ and R₇ are each methyl and m is 2, 3 or4; most preferably m is 3.

R₂ in graphic formulae I, II and III is the group, --C(O)W or --CH₂ OH,W being --OR₈ or --N(R₉)R₁₀, wherein R₈ is hydrogen, allyl, C₁ -C₆alkyl, e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl, phenyl,mono(C₁ -C₆)alkyl substituted phenyl, mono(C₁ -C₆)alkoxy-substitutedphenyl, phenyl(C₁ -C₃)alkyl, mono(C₁ -C₆)alkoyl substituted phenyl(C₁-C₃)alkyl, C₁ -C₆ alkoxy(C₂ -C₄)alkyl, or C₁ -C₆ haloalkyl; and R₉ andR₁₀ may each be selected from the group consisting of hydrogen, C₁ -C₆alkyl, C₅ -C₇ cycloalkyl, phenyl and mono- or di-substituted phenyl. Thephenyl substituents may be C₁ -C₆ alkyl and C₁ -C₆ alkoxy and the halosubstituents may be chloro or fluoro.

More preferably, R₂ is the group, --C(O)W, W being the groups --OR₈ or--N(R₉)R₁₀, wherein R₈ is hydrogen, C₁ -C₄ alkyl, phenyl, mono(C₁-C₄)alkyl substituted phenyl, mono(C₁ -C₄)alkoxy substituted phenyl,phenyl(C₁ -C₂)alkyl, mono(C₁ -C₄)alkyl substituted phenyl(C₁ -C₂)alkyl,mono(C₁ -C₄)alkoxy substituted phenyl(C₁ -C₂)alkyl, mono(C₁-C₄)alkoxy(C₂ -C₃)alkyl, or C₁ -C₄ haloalkyl; and R₉ and R₁₀ may each beselected from the group consisting of hydrogen, C₁ -C₄ alkyl, C₅ -C₇cycloalkyl, phenyl and mono- or di-substituted phenyl. The phenylsubstituents may be selected from C₁ -C₄ alkyl and C₁ -C₄ alkoxy, andthe halo substituents may be chloro or fluoro. Most preferably, R₂ isthe group --C(O)W, W being the group --OR₈, wherein R₈ is a C₁ -C₃alkyl.

Each R₃ in graphic formula I is C₁ -C₆ alkyl, C₃ -C₇ cycloalkyl,substituted or unsubstituted phenyl, or the group --OR₁₁, wherein R₁₁ ishydrogen or C₁ -C₆ alkyl, said phenyl substituents each being selectedfrom C₁ -C₆ alkyl or C₁ -C₆ alkoxy, and n is the integer 0, 1 or 2.Preferably, each R₃ is C₁ -C₃ alkyl, C₃ -C₅ cycloalkyl, substituted orunsubstituted phenyl or --OR₁₁, wherein R₁₁ is hydrogen or C₁ -C₃ alkyl,said phenyl substituents each being C₁ -C₃ alkyl or C₁ -C₃ alkoxy and nis the integer 0 or 1.

B and B' in graphic formulae I, II and III may each be selected from thegroup consisting of:

(i) the unsubstituted, mono-, di- and tri-substituted aryl groups,phenyl and naphthyl;

(ii) the unsubstituted, mono- and di-substituted heteroaromatic groupspyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl,carbazolyl and fluorenyl, each of said aryl and heteroaromaticsubstituents in parts (i) and (ii) being selected from the groupconsisting of hydroxy, aryl, mono(C₁ -C₆)alkoxyaryl, di(C₁-C₆)alkoxyaryl, mono(C₁ -C₆)alkylaryl, di(C₁ -C₆)alkylaryl, bromoaryl,chloroaryl, fluoroaryl, C₃ -C₇ cycloalkylaryl, C₃ -C₇ cycloalkyl, C₃ -C₇cycloalkyloxy, C₃ -C₇ cycloalkyloxy(C₁ -C₆)alkyl, C₃ -C₇cycloalkyloxy(C₁ -C₆)alkoxy, aryl(C₁ -C₆)alkyl, aryl(C₁ -C₆)alkoxy,aryloxy, aryloxy(C₁ -C₆)alkyl, aryloxy(C₁ -C₆)alkoxy, mono- and di(C₁-C₆)alkylaryl(C₁ -C₆)alkyl, mono- and di(C₁ -C₆)alkoxyaryl(C₁ -C₆)alkyl,mono- and di(C₁ -C₆)alkylaryl(C₁ -C₆)alkoxy, mono- and di(C₁-C₆)alkoxyaryl(C₁ -C₆)alkoxy, amino, mono(C₁ -C₆)alkylamino, di(C₁-C₆)alkylamino, diarylamino, N-(C₁ -C₆)alkylpiperazino,N-arylpiperazino, aziridino, indolino, piperidino, arylpiperidino,morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino,pyrryl, C₁ -C₆ alkyl, C₁ -C₆ bromoalkyl, C₁ -C₆ chloroalkyl, C₁ -C₆fluoroalkyl, C₁ -C₆ alkoxy, mono(C₁ -C₆)alkoxy(C₁ -C₄)alkyl, acryloxy,methacryloxy, bromo, chloro and fluoro;

(iii) the groups represented by the following graphic formulae: ##STR5##wherein E may be carbon or oxygen and D may be oxygen or substitutednitrogen, provided that when D is substituted nitrogen, E is carbon,said nitrogen substituents being selected from the group consisting ofhydrogen, C₁ -C₆ alkyl and C₂ -C₆ acyl; each R₁₂ is C₁ -C₆ alkyl, C₁ -C₆alkoxy, hydroxy, bromo, chloro or fluoro; R₁₃ and R₁₄ are each hydrogenor C₁ -C₆ alkyl; and p is the integer 0, 1 or 2;

(iv) C₁ -C₆ alkyl, C₁ -C₆ bromoalkyl, C₁ -C₆ chloroalkyl, C₁ -C₆fluoroalkyl, C₁ -C₆ alkoxy(C₁ -C₄)alkyl, C₃ -C₆ cycloalkyl, mono(C₁-C₆)alkoxy(C₃ -C₆)cycloalkyl, mono(C₁ -C₆)alkyl(C₃ -C₆)cycloalkyl,bromo(C₃ -C₆)cycloalkyl, chloro(C₃ -C₆)cycloalkyl and fluoro(C₃-C₆)cycloalkyl; and

(v) the group represented by the following graphic formula: ##STR6##wherein X in graphic formula VIc may be hydrogen or C₁ -C₄ alkyl and Yin graphic formula VIc may be selected from the unsubstituted, mono-,and di-substituted members of the group consisting of naphthyl, phenyl,furanyl and thienyl, each of said group substituents in this part (v)being C₁ -C₄ alkyl, C₁ -C₄ alkoxy, bromo, fluoro or chloro; or

(vi) B and B' taken together form fluoren-9-ylidene, mono- ordi-substituted fluoren-9-ylidene or form a member selected from thegroup consisting of saturated C₃ -C₁₂ spiro-monocyclic hydrocarbonrings, e.g., cyclopropylidene, cycloheptylidene, cycloocntylidene,cyclononylidene, cyclodecylidene cycloundecylidene andcyclododecylidene; cyclodecylidene cycloundecylidene andcyclododecylidene; saturated C₇ -C₁₂ spiro-bicyclic hydrocarbon rings,e.g., bicyclo 2.2.1!heptylidene, i.e., norbornylidene, 1,7,7-trimethylbicyclo 2.2.1!heptylidene, i.e., bornylidene, bicyclo 3.2.1!octylidene,bicyclo 3.3.1!nonan-9-ylidene and bicyclo 4.3.2!undecane and saturatedC₇ -C₁₂ spiro-tricyclic hydrocarbon rings, e.g., tricyclo 2.2.1.0²,6!heptylidene and tricyclo 3.3.1.1³,7 !decylidene, i.e., adamantylidene,and tricyclo 5.3.1.1²,6 !dodecylidene, each of said fluoren-9-ylidenesubstituents being selected from the group consisting of C₁ -C₄ alkyl,C₁ -C₄ alkoxy, bromo, fluoro and chloro.

More preferably, B and B' are each selected from the group consistingof: (i) phenyl, mono-substituted phenyl and di-substituted phenyl,preferably substituted in the meta and/or para positions; (ii) theunsubstituted, mono- and di-substituted heteroaromatic groups furanyl,benzofuran-2-yl, thienyl, benzothien-2-yl, dibenzofuran-2-yl anddibenzothien-2-yl, each of said phenyl and heteroaromatic substituentsin (i) and (ii) being selected from the group consisting of hydroxy,aryl, aryloxy, aryl(C₁ -C₃)alkyl, amino, mono(C₁ -C₃)alkylamino, di(C₁-C₃)alkylamino, N-(C₁ -C₃)alkylpiperazino, indolino, piperidino,morpholino, pyrryl, C₁ -C₃ alkyl, C₁ -C₃ chloroalkyl, C₁ -C₃fluoroalkyl, C₁ -C₃ alkoxy, mono(C₁ -C₃)alkoxy(C₁ -C₃)alkyl, fluoro andchloro; (iii) the groups represented by the graphic formulae VIa andVIb, wherein E is carbon and D is oxygen, R₁₂ is C₁ -C₃ alkyl or C₁ -C₃alkoxy, R₁₃ and R₁₄ are each hydrogen or C₁ -C₄ alkyl; and p is theinteger 0 or 1; (iv) C₁ -C₄ alkyl; and (v) the group represented by thegraphic formula VIc wherein X is hydrogen or methyl and Y is phenyl ormono-substituted phenyl, said phenyl substituent being selected from thegroup consisting of C₁ -C₃ alkyl, C₁ -C₃ alkoxy and fluoro; or (vi) Band B' taken together form fluoren-9-ylidene, mono-substitutedfluoren-9-ylidene or a member selected from the group consisting ofsaturated C₃ -C₈ spiro-monocyclic hydrocarbon saturated C₇ -C₁₀spiro-tricyclic hydrocarbon rings, sand fluoren-9-ylidene substituentbeing selected from the group consisting of C₁ -C₃ alkyl, C₁ -C₃ alkoxy,fluoro and chloro.

Most preferably, B and B' are each selected from the group consisting of(i) phenyl, mono- and di-substituted phenyl; (ii) the unsubstituted,mono- and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl,thienyl and benzothien-2-yl, each of said phenyl and heteroaromaticsubstituents in (i) and (ii) being selected from the group consisting ofhydroxy, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, aryl, morpholino, fluoro andchloro; and (iii) the group represented by graphic formula VIa, whereinE is carbon and D is oxygen, R₁₂ is C₁ -C₃ alkyl or C₁ -C₃ alkoxy, R₁₃and R₁₄ are each hydrogen or C₁ -C₃ alkyl, and p is the integer 0 or 1;or (iv) B and B' taken together form fluoren-9-ylidene, adamantylidene,bornylidene, norbornylidene or bicyclo 3.3.1!nonan-9-ylidene.

Compounds represented by graphic formula I may be prepared by thefollowing steps. In Reaction A, an alkyl magnesium halide reagent isreacted with a secondary amine corresponding to the R₁ group in graphicformulae I, II and III and represented by graphic formula VII in thepresence of tetrahydrofuran (THF) to form the correspondinghalomagnesium amide represented by graphic formula VIII wherein Z is ahalide including bromide, chloride and iodide. ##STR7##

In Reaction B, the halomagnesium amide represented by graphic formulaVIII is reacted with the 2H-naphtho 1,2-b!pyran represented by graphicformula IX in the presence of THF and quenched with water to formcompounds represented by graphic formula Ia. In graphic formula IX, R₁₁is methyl. The compound represented by graphic formula IX may beprepared by coupling a substituted naphthol with a propargyl alcohol.This procedure is described in U.S. Pat. No. 5,458,814, column 5, line10 to column 7, line 67. The propargyl alcohol may be prepared accordingto the methods disclosed in U.S. Pat. No. 5,645,767, column 5, line 8 tocolumn 6, line 30. The aforesaid patents are incorporated herein in totoby reference. ##STR8##

As shown in Reaction C, when R₂ is methoxycarbonyl, the compoundsrepresented by graphic formula Ia may be reduced by reaction thereofwith a reagent, preferably lithium aluminum hydride, in THF to form thecompounds represented by graphic formula Ib. The free base compoundsrepresented by graphic formulae Ia and Ib are acidified to produce thecorresponding quaternary ammonium salts which are water soluble.##STR9##

Examples of the free base of contemplated 2H-naphtho 1,2-b!pyrans withinthe scope of the invention are the following:

(a) 2,2-bis(4-methoxyphenyl)-5-methoxycarbonyl-6-bis(3-dimethylaminopropyl)amino-2H-naphtho 1,2-b!pyran;

(b)2,2-diphenyl-5-methoxycarbonyl-6-(3-dimethylaminopropyl)methylamino-2H-naphtho1,2-b!pyran; and

(c)2,2-diphenyl-5-methylol-6-(3-dimethylaminopropyl)methylamino-2H-naphtho1,2-b!pyran.

Compounds represented by graphic formula II may be prepared by firstfollowing Reaction A to produce the halomagnesium amide represented bygraphic formula VIII. In reaction D, the 3H-naphtho 2,1-b!pyranrepresented by graphic formula X is reacted with the halomagnesium amiderepresented by graphic formula VIII in the presence of THF and quenchedwith water to form compounds represented by graphic formula IIa. Ingraphic formula X, R₁₁ is methyl. The compound represented by graphicformula X may be prepared by coupling methyl-3,7-dihydroxy-2-naphthoatewith propargyl alcohol. This procedure is disclosed in U.S. Pat. No.5,466,398, column 3, line 65 to column 9, line 28, incorporated hereinin toto by reference. The propargyl alcohol may be prepared according tothe methods disclosed in U.S. Pat. No. 5,645,767. The compoundsrepresented by graphic formula IIa are acidified to produce thecorresponding quaternary ammonium salts which are water soluble.##STR10##

Examples of the free base form of contemplated 3H!-naphtho 2,1-b!pyranswithin the scope of the invention are the following:

(a) 3,3-bis(4-methoxyphenol)-8-bis(3-dimethylaminopropyl)amino-3H-naphtho 2,1-b!pyran; and

(b) 3,3-diphenyl-8-(3-dimethylaminopropyl)methylamino-3H-naphtho2,1-b!pyran.

Compounds represented by graphic formula III may be prepared by firstfollowing Reaction A to produce the halomagnesium amide represented bygraphic formula VIII. In Reaction E, the dihydroxybenzoic acidrepresented by graphic formula XI is reacted with an alkyl halide or abenzylhalide, e.g., methyl iodide, ethyl chloride, benzyl bromide, etc.,(R" halide) in the presence of ethyldiisopropyl amine or sodiumbicarbonate in a suitable solvent such as anhydrous dimethylformamide(DMF) to form the corresponding dihydroxybenzoate represented by graphicformula XII. ##STR11##

In Reaction F, propargyl alcohol represented by graphic formula XIIIhaving the B and B' substituents defined above for graphic formulae I,II and III is coupled with the dihydroxybenzoate represented by graphicformula XII in the presence of p-toluene sulfonic acid (PTSA) in asuitable solvent such as toluene to produce benzopyrans represented bygraphic formula XIV. The propargyl alcohol represented by graphicformula XIII may be prepared according to the method described in U.S.Pat. No. 5,645,767, column 5, line 8 to column 6, line 30. Thebenzopyrans represented by graphic formula XIV are alkylated, via, e.g.,reaction with methyl iodide in the presence of anhydrous potassiumcarbonate in a suitable solvent such as anhydrous acetone to form thealkoxy substituted benzopyran compounds represented by graphic formulaXV. Alkylating reactions are further described in Organic Synthesis,Vol. 31, pages 90-93, John Wiley and Sons, Inc., New York, N.Y. (1951).##STR12##

In Reaction G, the benzopyran represented by graphic formula XV isreacted with the halomagnesium amide represented by graphic formula VIIIin the presence of THF and quenched with water to form compoundsrepresented by graphic formula IIIA. The alkoxycarbonyl group (--COOR")in graphic formula IIIA may be reduced by reaction with a reagent,preferably, lithium aluminum hydride, in THF to form the correspondinghydroxy compounds. The compounds represented by graphic formula IIIA areacidified to form the corresponding quaternary ammonium salts which arewater soluble. ##STR13##

An example of the free base form of a contemplated benzopyran within thescope of the invention is2,2-diphenyl-5-methoxycarbonyl-6-bis(3-dimethylaminopropyl)amino-2H-benzopyran.

Aqueous solutions of the inventive photochromic compounds may be used toincorporate the compounds into an article. The water solubility of thenaphthopyrans and benzopyrans of the present invention depends on theratio of the number of hydrophilic moieties to the number of hydrophobicmoieties thereon. The quaternary ammonium salt of the aminofunctionality identified as the R₁ substituent on these compounds ishydrophilic. By water soluble it is meant that a measurable amount ofthe photochromic compounds of the present invention is soluble in water.The compounds of the present invention having only two quaternaryammonium salt functionalities in the R₁ group are soluble in water atabout 1 gram per liter. It is contemplated that the inventive compoundshaving more than two quaternary ammonium salt functionalities in the R₁group are more water soluble. Thus, the compounds of the presentinvention are at least water soluble at one gram per liter. The presentinvention further includes the corresponding free bases of thequaternary ammonium salts represented by graphic formulae I, II and III.

The water soluble compounds represented by graphic formulae I, II andIII may be used in those applications in which organic photochromicsubstances may be employed, such as optical lenses, e.g., visioncorrecting ophthalmic lenses and plano lenses, face shields, goggles,visors, camera lenses, windows, automotive windshields, aircraft andautomotive transparencies, e.g., T-roofs, sidelights and backlights,plastic films and sheets, textiles and coatings, e.g., coatingcompositions. Coating compositions are defined herein to include paints,i.e., a pigmented liquid or paste used for the decoration, protectionand/or the identification of a substrate, and inks, i.e., a pigmentedliquid or paste used for writing and printing on substrates. Substratesare materials to which the coating composition is applied, of any typesuch as, paper, glass, ceramics, wood, masonry, textiles, metals andorganic polymeric materials. Coating compositions may be used to produceverification marks on security documents, e.g., documents such asbanknotes, passport and drivers' licenses for which authentication orverification of authenticity may be desired. The water solublephotochromic compounds of the present invention may also be used astracers, e.g., in flow studies by injecting the inventive compounds intoa portion of an aqueous flow system, exposing the flow system to theappropriate UV light which will induce a color change in the inventivecompounds and monitoring their distribution in the flow system.

The 2H-naphtho- 1,2-b!pyrans represented by graphic formula I exhibitcolor changes from colorless to colors ranging from yellow tored/purple. The 3H-naphtho 2,1-b!pyrans represented by graphic formulaII exhibit color changes from colorless to colors ranging from yellow toorange and red. The benzopyrans represented by graphic formula IIIexhibit color changes from colorless to colors ranging from red topurple.

It is contemplated that the photochromic naphthopyrans and benzopyransof the present invention may each be used alone in the acid salt form,in combination with the acid salts of other naphthopyrans andbenzopyrans of the present invention, or as the corresponding free basesin combination with one or more other appropriate complementary organicphotochromic materials, i.e., organic photochromic compounds having atleast one activated absorption maxima within the range of between about400 and 700 nanometers (or substances containing the same) and whichcolor when activated to an appropriate hue. The photochromic compoundsof the present invention may be associated with, incorporated in, e.g.,dissolved or dispersed in, a polymeric organic host material used toprepare photochromic articles.

Other than where otherwise indicated, all numbers expressingwavelengths, quantities of ingredients or reaction conditions usedherein are to be understood as modified in all instances by the term"about".

Examples of complementary organic photochromic compounds includeindenonaphthopyrans, chromenes and oxazines, naphthopyrans, substituted2H-phenanthro 4,3-b!pyran and 3H-phenanthro 1,2-b!pyran compounds, otherbenzopyran compounds having substituents at the 2-position of the pyranring and mixtures of such photochromic compounds. Many of suchphotochromic compounds are described in the open literature, e.g., U.S.Pat. Nos. 3,562,172; 3,567,605; 3,578,602; 4,215,010; 4,342,668;4,816,584; 4,818,096; 4,826,977; 4,880,667; 4,931,219; 5,066,818;5,238,981; 5,274,132; 5,384,077; 5,405,958; 5,429,774; 5,458,814,5,466,398; 5,514,817; 5,552,090; 5,552,091; 5,565,147; 5,573,712;5,578,252; WO 96 14596 and Japanese Patent Publication 62/195383.Spiro(indoline)pyrans are also described in the text, Techniques inChemistry, Volume III, "Photochromism", Chapter 3, Glenn H. Brown,Editor, John Wiley and Sons, Inc., New York, 1971.

The disclosures relating to such photochromic compounds in theaforedescribed patents are incorporated herein, in toto, by reference.The photochromic articles of the present invention may contain onephotochromic compound or a mixture of photochromic compounds, asdesired.

Each of the photochromic substances described herein may be used inamounts (or in a ratio) such that an organic host material to which thephotochromic compounds or mixture of compounds is applied or in whichthey are incorporated exhibits a desired resultant color, e.g., asubstantially neutral color when activated with unfiltered sunlight,i.e., as near a neutral color as possible given the colors of theactivated photochromic compounds. Neutral gray and neutral brown colorsare preferred.

A neutral gray color exhibits a spectrum that has relatively equalabsorption in the visible range between 400 and 700 nanometers. Aneutral brown color exhibits a spectrum in which the absorption in the400-550 nanometer range is moderately larger than in the 550-700nanometer range. An alternative way of describing color is in terms ofits chromaticity coordinates, which describe the qualities of a color inaddition to its luminance factor, i.e., its chromaticity. In the CIEsystem, the chromaticity coordinates are obtained by taking the ratiosof the tristimulus values to their sum, e.g., x=X/(X+Y+Z) andy=Y/(X+Y+Z). Color as described in the CIE system can be plotted on achromaticity diagram, usually a plot of the chromaticity coordinates xand y. See pages 47-52 of Principles of Color Technology, by F. W.Billmeyer, Jr., and Max Saltzman, Second Edition, John Wiley and Sons,N.Y. (1981). As used herein, a near neutral color is one in which thechromaticity coordinate values of "x" and "y" for the color are withinthe following ranges (D65 illuminant): x=0.260 to 0.400, y=0.280 to0.400 following activation to 40 percent luminous transmission byexposure to solar radiation (Air Mass 1 or 2).

The amount of the photochromic naphthopyrans and/or benozpyrans to beapplied to or incorporated into a carrier or host material is notcritical provided that a sufficient amount is used to produce aphotochromic effect discernible to the naked eye upon activation.Generally such amount can be described as a photochromic amount. Theparticular amount used depends often upon the intensity of color desiredupon irradiation thereof and upon the method used to incorporate orapply the photochromic compounds. Typically, the more photochromiccompound applied or incorporated, the greater is the color intensity upto a certain limit.

The relative amounts of the aforesaid photochromic compounds used willvary and depend in part upon the relative intensities of the color ofthe activated species of such compounds, and the ultimate color desired.Generally, the amount of total photochromic compound incorporated intoor applied to a photochromic optical host material may range from about0.05 to about 1.0, e.g., from 0.1 to about 0.45, milligrams per squarecentimeter of volume or surface to which the photochromic compounds isincorporated or applied.

The photochromic naphthopyrans and benzopyrans of the present inventionmay be associated with, applied to or incorporated within the hostmaterial by various methods described in the art. Such methods includedissolving or dispersing the photochromic compounds in water or organicpolymeric host material, e.g., casting it in place by adding thephotochromic compounds to the monomeric host material prior topolymerization; imbibition of the photochromic compounds into the hostmaterial by immersion of the host material in a hot solution of thephotochromic compounds or by thermal transfer; providing thephotochromic compounds as a separate layer between adjacent layers ofthe host material, e.g., as a part of a polymeric film; and applying thephotochromic compounds as part of a coating placed on the surface of thehost material. The term "imbibition" or "imbibe" is intended to mean andinclude permeation of the photochromic compounds alone into the hostmaterial, solvent assisted transfer of the photochromic compounds into aporous polymer, vapor phase transfer, and other such transfermechanisms.

Compatible (chemically and color-wise) tints, i.e., dyes, may be appliedto the host material to achieve a more aesthetic result, for medicalreasons, or for reasons of fashion. The particular dye selected willvary and depend on the aforesaid need and result to be achieved. In oneembodiment, the dye may be selected to complement the color resultingfrom the activated photochromic compounds, e.g., to achieve a moreneutral color or absorb a particular wavelength of incident light. Inanother embodiment, the dye may be selected to provide a desired hue tothe host material when the photochromic compounds are in an unactivatedstate.

The host material will usually be transparent, but may be translucent oreven opaque. The host material need only be pervious to that portion ofthe electromagnetic spectrum, which activates the photochromicsubstance, i.e., that wavelength of ultraviolet (UV) light that producesthe open or colored form of the substance and that portion of thevisible spectrum that includes the absorption maximum wavelength of thesubstance in its UV activated form, i.e., the open form. Preferably, thehost color should not be such that it masks the color of the activatedform of the photochromic compounds, i.e., so the change in color isreadily apparent to the observer.

The photochromic compounds of the present invention are soluble in waterwhen acidified to form quaternary salts. Aqueous solutions of thequaternary salts of the photochromic compounds may be used to dispersethe photochromic compounds into an organic polymeric host material orother materials such as textiles and ink or paint bases. Alternatively,the free base form of the photochromic compounds may be dissolved in anorganic solvent. The organic solvent may be selected from the groupconsisting of benzene, toluene, methyl ethyl ketone, acetone, ethanol,tetrahydrofurfuryl alcohol, N-methyl pyrrolidinone, 2-methoxyethylether, xylene, cyclohexane, 3-methyl cyclohexanone, ethyl acetate,tetrahydrofuran, methanol, methyl propitiate, ethylene glycol andmixtures thereof. Preferably, the organic solvent is selected from thegroup consisting of acetone, ethanol, tetrahydrofurfuryl alcohol,2-methoxyethyl ether, 3-methyl cyclohexanone, N-methyl pyrrolidinone andmixtures thereof. Preferably, the organic polymeric host material is asolid transparent or optically clear material, e.g., materials suitablefor optical applications, such as plano and ophthalmic lenses, windows,automotive transparencies, e.g., windshields, aircraft transparencies,plastic sheeting, polymeric films, etc. Examples of polymeric organichost materials are polymers prepared from individual monomers ormixtures of monomers selected from the following groups:

(a) diacrylate or dimethacrylate compounds represented by graphicformula XVI: ##STR14## wherein R₁₅ and R₁₆ may be the same or differentand are hydrogen or methyl, and V is methylene (CH₂) and t is an integerof from 1 to 20;

(b) diacrylate or dimethacrylate compounds represented by graphicformula XVII: ##STR15## wherein L is CH₂ CH(R₁₆), or (CH₂)_(v), whereinv is an integer selected from the group consiting of 1, 3 and 4, and sis an integer of from 1 to 50; and

(c) an acrylate or a methacrylate compound having an epoxy grouprepresented by graphic formula XVIII: ##STR16## wherein R₁₈ is hydrogenor methyl.

In graphic formulae XVI, XVII and XVIII, like letters used with respectto the definitions of different substituents have the same meaning.

Examples of diacrylate or dimethacrylate compounds represented bygraphic formulae XVI include butanediol di(meth)acrylate, hexanedioldi(meth)acrylate and nonanediol di(meth)acrylate, and represented bygraphic formula XVII include diethylene glycol dimethacrylate,triethylene glycol dimethacrylate, etc., butanediol dimethacrylate andpoly(oxyalkylene dimethacrylates), e.g., polyethylene glycol (600)dimethacrylate. Examples of acrylate or methacrylate compoundsrepresented by graphic formula XVIII include glycidyl acrylate andglycidyl methacrylate.

Further examples of polymeric organic host materials which may be usedwith the photochromic compounds described herein include: polymers,i.e., homopolymers and copolymers, of the monomers and mixtures ofmonomers represented by graphic formulae XVI, XVII and XVIII, bis(allylcarbonate) monomers, diisopropenyl benzene monomers, ethoxylatedbisphenol A dimethacrylate monomers, ethylene glycol bismethacrylatemonomers, poly(ethylene glycol) bismethacrylate monomers, ethoxylatedphenol bismethacrylate monomers, alkoxylated polyhydric alcoholpolyacrylate monomers, such as ethoxylated trimethylol propanetriacrylate monomers, urethane acrylate monomers, such as thosedescribed in U.S. Pat. No. 5,373,033, and vinylbenzene monomers, such asthose described in U.S. Pat. No. 5,475,074 and styrene; polymers, i.e.,homopolymers and copolymers, of polyfunctional, e.g., mono-, di- ormulti-functional, acrylate and/or methacrylate monomers, poly(C₁ -C₁₂alkyl methacrylates), such as poly(methyl methacrylate),poly(alkoxylated phenol methacrylates), cellulose acetate, cellulosetriacetate, cellulose acetate propionate, cellulose acetate butyrate,poly vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride),poly(vinylidene chloride), polyurethanes, thermoplastic polycarbonates,polyesters, poly(ethylene terephthalate), polystyrene, poly(alphamethylstyrene), copoly(styrene-methyl methacrylate),copoly(styrene-acrylonitrile), polyvinylbutyral and polymers, i.e.,homopolymers and copolymers, of diallylidene pentaerythritol,particularly copolymers with polyol (allyl carbonate) monomers, e.g.,diethylene glycol bis(allyl carbonate), and acrylate monomers, e.g.,ethyl acrylate, butyl acrylate.

Transparent copolymers and blends of transparent polymers are alsosuitable as host materials. Preferably, the host material is anoptically clear polymerized organic material prepared from athermoplastic polycarbonate resin, such as the carbonate-linked resinderived from bisphenol A and phosgene, which is sold under thetrademark, LEXAN; a polyester, such as the material sold under thetrademark, MYLAR; a poly(methyl methacrylate), such as the material soldunder the trademark, PLEXIGLAS; polymerizates of a polyol(allylcarbonate) monomer, especially diethylene glycol bis(allyl carbonate),which monomer is sold under the trademark CR-39, and polymerizates ofcopolymers of a polyol (allyl carbonate), e.g., diethylene glycolbis(allyl carbonate), with other copolymerizable monomeric materials,such as copolymers with vinyl acetate, e.g., copolymers of from 80-90percent diethylene glycol bis(allyl carbonate) and 10-20 percent vinylacetate, particularly 80-85 percent of the bis(allyl carbonate) and15-20 percent vinyl acetate, and copolymers with a polyurethane havingterminal diacrylate functionality, as described in U.S. Pat. Nos.4,360,653 and 4,994,208; and copolymers with aliphatic urethanes, theterminal portion of which contain allyl or acrylyl functional groups, asdescribed in U.S. Pat. No. 5,200,483; poly(vinyl acetate),polyvinylbutyral, polyurethane, polymers of members of the groupconsisting of diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers, ethoxylated bisphenol A dimethacrylate monomers,ethylene glycol bismethacrylate monomers, poly(ethylene glycol)bismethacrylate monomers, ethoxylated phenol bismethacrylate monomersand ethoxylated trimethylol propane triacrylate monomers; celluloseacetate, cellulose propionate, cellulose butyrate, cellulose acetatebutyrate, polystyrene and copolymers of styrene with methylmethacrylate, vinyl acetate and acrylonitrile.

More particularly, contemplated is use of the photochromic naphthopyransand benzopyrans of the present invention with optical organic resinmonomers used to produce optically clear polymerizates, i.e., materialssuitable for optical applications, such as for example plano andophthalmic lenses, windows, and automotive transparencies. Suchoptically clear polymerizates may have a refractive index that may rangefrom about 1.48 to about 1.75, e.g., from about 1.495 to about 1.66.Specifically contemplated are optical resins sold by PPG Industries,Inc. under the CR-designation, e.g., CR-307 and CR-407.

The water soluble photochromic compounds of the present invention offerhandling and processing advantages not achieved by water insolublephotochromic compounds. In particular, the use of hazardous organicsolvents as carriers for photochromic compounds is avoided. As a finalstep in the preparation of optical lenses and other transparentpolymeric articles, the surfaces thereof must be cleaned of excessphotochromic compounds. Because the photochromic compounds of thepresent invention are water soluble in an acidic environment, suchsurfaces may be cleaned with a dilute acid.

It is further contemplated that the photochromic naphthopyrans andbenzopyrans of the present invention may be used in aqueous or organicbased inks or paints. The inventive photochromic compounds may beincorporated into different printing inks and paints for application onvarious articles including printed documents, printed textiles, andpainted or coated articles for functional or decorative purposes.Hereafter, by the term ink it is meant all inks, paints and the like forapplication to another article or incorporation into anothercomposition. The inventive photochromic compounds should (a) provide ameasurable photochromic response when incorporated into an ink andexposed to a source of activating light, (b) be soluble within the inkand (c) be chemically compatible with the base ink composition.

Although the present invention has been described with respect tophotochromic 2H-naphtho 1,2-b!pyrans, 3H-naphtho 2,1-b!pyrans andbenzopyrans, other related photochromic compounds could be made watersoluble via amination in a similar manner. Such other relatedphotochromic compounds include compounds having an alkoxy group at aposition ortho to an ester substituent suitable for coupling with ahalomagnesium amide and subsequent acidification thereof to produce awater soluble amino-substituted photochromic compound.

The present invention is more particularly described in the followingexamples which are intended as illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art.

EXAMPLE 1 Step 1

Bis(3-dimethylaminopropyl)amine (4 grams) was added to a reaction flaskcontaining 50 milliliters (mL) of anhydrous tetrahydrofuran (THF) andstirred at room temperature. Methyl magnesium bromide in astoichiometric amount (7 mL of a 3 molar hexane solution) was added andstirred for one hour. The reaction mixture containing bromomagnesiumbis(3-dimethylaminopropyl)amide was not purified but used directly inthe next step.

Step 2

2,2-bis(4-methoxyphenyl)-5-methoxycarbonyl-6-methoxy-2H-naphtho1,2-b!pyran (3 grams) was added to a flask containing anhydroustetrahydrofuran (5 mL). The naphthopyran solution was added to thereaction mixture of Step 1 and stirred at room temperature for twohours. Water (100 mL) was slowly added and stirred for one half hour.The resulting mixture was extracted three times with diethyl ether (25mL each). The three organic extracts were combined and washed withdistilled water. The resulting diethyl ether solution was extractedthree times with a 10 weight percent hydrochloric acid solution (25 mLeach). The three acid solutions were combined and neutralized with a 10weight percent sodium hydroxide solution. The resulting neutral solutionwas extracted three times with diethyl ether (25 mL each). The threeorganic extracts were combined, washed with water and dried overanhydrous magnesium sulfate. The solvent was evaporated leaving 2 gramsof an oily product. A nuclear magnetic resonance (NMR) spectrum showedthe product to have a structure consistent with2,2-bis(4-methoxyphenyl)-5-methoxycarbonyl-6-bis(3-dimethylaminopropyl)amino-2H-naphtho1,2-b!pyran.

Step 3

The2,2-bis(4-methoxyphenyl)-5-methoxycarbonyl-6-bis(3-dimethylaminopropyl)amino-2H-naphtho1,2-b!pyran prepared in Step 2 was added to a reaction flask containinganhydrous diethyl ether. The solution was bubbled with dry hydrochloricacid gas until a white solid separated out. The solid was removed fromthe solution by filtration, washed with anhydrous diethyl ether, washedwith hexane, dried and was determined to have a water solubility of 1gram per liter. Upon acidification and illumination with ultravioletlight, an aqueous solution of the product exhibited a red-purple color.

EXAMPLE 2 Step 1

The procedure of Step 1 of Example 1 was followed except thatN,N',N'-trimethyl-1,3-propanediamine was used in place ofbis(3-dimethylaminopropyl)amine to produce a reaction mixture containingbromomagnesium N,N',N'-trimethyl-1,3-propanediamide.

Step 2

2,2-diphenyl-5-methoxycarbonyl-6-methoxy-2H-naphtho 1,2-b!pyran (3grams) was added to a flask containing anhydrous tetrahydrofuran (10mL). The resulting naphthopyran solution was added to the reactionmixture of Step 1 and stirred at room temperature for two hours. Water(100 mL) was added to the reaction mixture and the resulting mixture wasextracted three times with diethyl ether (25 mL each). The organicextracts were combined, washed with water, and dried over anhydrousmagnesium sulfate. The solvent was evaporated leaving an oily product.The oily product was induced to crystallize from diethyl ether. Thesolid product was suction filtered, washed with hexane and air dried,leaving 2.5 grams of the recovered product. The recovered product had amelting point of 154°-155° C. A nuclear magnetic resonance (NMR)spectrum showed the product to have a structure consistent with2,2-diphenyl-5-methoxycarbonyl-6-(3-dimethylaminopropyl)methylamino-2H-naphtho1,2-b!pyran. Upon acidification and illumination with ultraviolet light,an aqueous solution of the product exhibited a red color.

EXAMPLE 3

The2,2-diphenyl-5-methoxycarbonyl-6-(3-dimethylaminopropyl)methylamino-2H-naphtho1,2-b!pyran (2 grams) prepared in Example 2, Step 2, was added to areaction flask containing anhydrous tetrahydrofuran (50 mL) and stirredat room temperature. Lithium aluminum hydride (1 gram) was added slowlyto the flask and stirred for two hours. A 5 weight percent hydrochloricacid solution (100 mL) was added and stirred for one half hour. Theaqueous layer was separated, washed with diethyl ether (25 mL), andneutralized with a 10 weight percent sodium hydroxide solution. Theresulting neutral solution was extracted ten times with diethyl ether(20 mL each). The organic extracts were combined, washed with water, anddried over anhydrous magnesium sulfate. The solvent was evaporatedleaving 1 gram of an oily product. A nuclear magnetic resonance (NMR)spectrum showed the product to have a structure consistent with2,2-diphenyl-5-methylol-6-(3-dimethylaminopropyl)methylamino-2H-naphtho1,2-b!pyran. Upon acidification and illumination with ultraviolet light,an aqueous solution of the product exhibited a red color.

The present invention has been described with reference to specificdetails of particular embodiments thereof. It is not intended that suchdetails be regarded as limitations upon the scope of the inventionexcept insofar as to the extent that they are included in theaccompanying claims.

What is claimed is:
 1. A compound represented by the following graphicformulae: ##STR17## or its free base wherein, (a) R₁ is the grouprepresented by the following graphic formula ##STR18## wherein R₄ is C₁-C₃ alkyl, phenyl(C₁ -C₃)alkyl, phenyl or R₅, A is an anion selectedfrom the group consisting of chloride, bromide, sulfate and phosphateand R₅ is the group represented by the following graphic formula:##STR19## wherein R₆ and R₇ are each C₁ -C₃ alkyl or C₁ -C₃alkylamino(C₁ -C₃)alkylamino; and m is 2, 3 or 4;(b) R₂ is the group,--C(O)W or --CH₂ OH, W being --OR₈ or --N(R₉)R₁₀, wherein R₈ is selectedfrom the group consisting of hydrogen, allyl, C₁ -C₆ alkyl, phenyl,mono(C₁ -C₆)alkyl substituted phenyl, mono(C₁ -C₆) alkoxy-substitutedphenyl, phenyl(C₁ -C₃)alkyl, mono(C₁ -C₆)alkyl substituted phenyl(C₁-C₃)alkyl, mono(C₁ -C₆)alkoxy substituted phenyl(C₁ -C₃)alkyl, C₁ -C₆alkoxy(C₂ -C₄)alkyl, and C₁ -C₆ haloalkyl, and wherein R₉ and R₁₀ areeach selected from the group consisting of hydrogen, C₁ -C₆ alkyl, C₅-C₇ cycloalkyl, phenyl and mono- or di-substituted phenyl, said phenylsubstituents being C₁ -C₆ alkyl or C₁ -C₆ alkoxy and said halosubstituents being chloro or fluoro; (c) each R₃ is C₁ -C₆ alkyl, C₃ -C₇cycloalkyl, substituted or unsubstituted phenyl or the group --OR₁₁,wherein R₁₁ is hydrogen or (C₁ -C₆)alkyl, said phenyl substituents beingselected from C₁ -C₆ alkyl o,r C₁ -C₆ alkoxy, and n is 0, 1 or 2; and(d) B and B' are each selected from the group consisting of:(i) theunsubstituted, mono-, di- and tri-substituted aryl groups, phenyl andnaphthyl; (ii) the unsubstituted, mono- and di-substitutedheteroaromatic groups pyridyl, furanyl, benzofuran-2-yl,benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl, each of saidaryl and heteroaromatic substituents in (d) (i) and (ii) being selectedfrom the group consisting of hydroxy, aryl, mono(C₁ -C₆)alkoxyaryl,di(C₁ -C₆)alkoxyaryl, mono(C₁ -C₆)alkylaryl, di(C₁ -C₆)alkylaryl,bromoaryl, chloroaryl, fluoroaryl, C₃ -C₇ cycloalkylaryl, C₃ -C₇cycloalkyl, C₃ -C₇ cycloalkyloxy, C₃ -C₇ cycloalkyloxy(C₁ -C₆)alkyl, C₃-C₇ cycloalkyloxy(C₁ -C₆)alkoxy, aryl(C₁ -C₆)alkyl, aryl(C₁ -C₆)alkoxy,aryloxy, aryloxy(C₁ -C₆)alkyl, aryloxy(C₁ -C₆)alkoxy, mono- and di(C₁-C₆)alkylaryl(C₁ -C₆)alkyl, mono- and di(C₁ -C₆)alkoxyaryl(C₁ -C₆)alkyl,mono- and di(C₁ -C₆)alkylaryl(C₁ -C₆)alkoxy, mono- and di(C₁-C₆)alkoxyaryl(C₁ -C₆)alkoxy, amino, mono(C₁ -C₆)alkylamino, di(C₁-C₆)alkylamino, diarylamino, N(C₁ -C₆)alkylpiperazino, N-arylpiperazino,aziridino, indolino, piperidino, arylpiperidino, morpholino,thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, C₁-C₆ alkyl, C₁ -C₆ bromoalkyl, C₁ -C₆ chloroalkyl, C₁ -C₆ fluoroalkyl, C₁-C₆ alkoxy, mono(C₁ -C₆)alkoxy(C₁ -C₄)alkyl, acryloxy, methacryloxy,bromo, chloro and fluoro; (iii) the groups represented by the followinggraphic formulae: ##STR20## wherein E is carbon or oxygen and D isoxygen or substituted nitrogen, provided that when D is substitutednitrogen, E is carbon, said nitrogen substituents being selected fromthe group consisting of hydrogen, C₁ -C₆ alkyl and C₂ -C₆ acyl; each R₁₂is C₁ -C₆ alkyl, C₁ -C₆ alkoxy, hydroxy, bromo, chloro or fluoro; R₁₃and R₁₄ are each hydrogen or C₁ -C₆ alkyl; and p is 0, 1 or 2; (iv) C₁-C₆ alkyl, C₁ -C₆ bromoalkyl, C₁ -C₆ chloroalkyl, C₁ -C₆ fluoroalkyl, C₁-C₆ alkoxy(C₁ -C₄)alkyl, C₃ -C₆ cycloalkyl, mono(C₁ -C₆)alkoxy(C₃-C₆)cycloalkyl, mono(C₁ -C₆)alkyl(C₃ -C₆)cycloalkyl, bromo(C₃-C₆)cycloalkyl, chloro(C₃ -C₆)cycloalkyl and fluoro(C₃ -C₆)cycloalkyl;and (v) the group represented by the following graphic formula:##STR21## wherein X is hydrogen or C₁ -C₄ alkyl and Y is selected fromthe unsubstituted, mono-, and di-substituted members of the groupconsisting of naphthyl, phenyl, furanyl and thienyl, each of said groupsubstituents in this part (v) being C₁ -C₄ alkyl, C₁ -C₄ alkoxy, bromo,fluoro or chloro; or (vi) B and B' taken together formfluoren-9-ylidene, mono- or di-substituted fluoren-9-ylidene or a memberselected from the group consisting of saturated C₃ -C₁₂ spiro-monocyclichydrocarbon rings, saturated C₇ -C₁₂ spiro-bicyclic hydrocarbon rings,and saturated C₇ -C₁₂ spiro-tricyclic hydrocarbon rings, each of saidfluoren-9-ylidene substituents being selected from the group consistingof C₁ -C₄ alkyl, C₁ -C₄ alkoxy, bromo, fluoro and chloro.
 2. Thecompound of claim 1 wherein:(a) R₁ is the group represented by thefollowing graphic formula: ##STR22## wherein R₄ is methyl or3-dimethylaminopropyl and R₅ is the group represented by the followinggraphic formula: ##STR23## wherein m is 2, 3 or 4; (b) R₂ is the group--C(O)W, W being the groups --OR₈ or --N(R₉)R₁₀, wherein R₈ is selectedfrom the group consisting of hydrogen, C₁ -C₄ alkyl, phenyl, mono (C₁-C₄)alkyl substituted phenyl, mono(C₁ -C₄)alkoxy substituted phenyl,phenyl(C₁ -C₂)alkyl, mono(C₁ -C₄)alkyl substituted phenyl(C₁ -C₂)alkyl,mono(C₁ -C₄)alkoxy substituted phenyl(C₁ -C₂)alkyl, mono(C₁-C₄)alkoxy(C₂ -C₃)alkyl, and C₁ -C₄ haloalkyl and wherein R₉ and R₁₀ areeach selected from the group consisting of hydrogen, C₁ -C₄ alkyl, C₅-C₇ cycloalkyl, phenyl and mono- or di-substituted phenyl, said phenylsubstituents being C₁ -C₄ alkyl or C₁ -C₄ alkoxy, said halo substituentsbeing chloro or fluoro; (c) each R₃ is hydrogen, C₁ -C₃ alkyl, C₃ -C₅cycloalkyl substituted or unsubstituted phenyl or --OR₁₁, wherein R₁₁ ishydrogen or C₁ -C₃ alkyl, said phenyl substituents being C₁ -C₃ alkyl orC₁ -C₃ alkoxy and n is 0 or 1; and (d) B and B' are each selected fromthe group consisting of:(i) phenyl, mono-substituted phenyl anddi-substituted phenyl; (ii) the unsubstituted, mono-substituted anddi-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl,benzothien-2-yl, dibenzofuran-2-yl, and dibenzothien-2-yl, each of -saidphenyl and heteroaromatic substituents in (d)(i) and (ii) being selectedfrom the group consisting of hydroxy, aryl, aryloxy, aryl(C₁ -C₃)alkyl,amino, mono(C₁ -C₃)alkylamino, di(C₁ -C₃)alkylamino, N(C₁-C₃)alkylpiperazino, indolino, piperidino, morpholino, pyrryl, C₁ -C₃alkyl, C₁ -C₃ chloroalkyl, C₁ -C₃ fluoroalkyl, C₁ -C₃ alkoxy, mono(C₁-C₃)alkoxy(C₁ -C₃)alkyl, fluoro and chloro; (iii) the groups representedby the following graphic formulae: ##STR24## wherein E is carbon and Dis oxygen, R₁₂ is C₁ -C₃ alkyl or C₁ -C₃ alkoxy, R₁₃ and R₁₄ are eachhydrogen or C₁ -C₄ alkyl; and p is 0 or 1; (iv) C₁ -C₄ alkyl; and (v)the group represented by the following graphic formula: ##STR25##wherein X is hydrogen or methyl and Y is phenyl or mono-substitutedphenyl, said phenyl substituent being selected from the group consistingof C₁ -C₃ alkyl, C₁ -C₃ alkoxy and fluoro; or (vi) B and B' takentogether form a fluoren-9 -ylidene, mono-substituted fluoren-9-ylideneor a member selected from the group consisting of saturated C₃ -C₈spiro-monocyclic hydrocarbon rings, saturated C₇ -C₁₀ spiro-bicyclichydrocarbon rings and saturated C₇ -C₁₀ spiro-tricyclic hydrocarbonrings, said fluoren-9-xylidene substituent being selected from the groupconsisting of C₁ -C₃ alkyl, C₁ -C₃ alkoxy, fluoro and chloro.
 3. Thecompound of claim 2 wherein(a) R₁ is the group represented by thefollowing graphic formula: ##STR26## wherein R₄ is methyl or3-dimethylaminopropyl and R₅ is 3-dimethylaminopropyl; (b) R₂ is thegroup --C(O)W, W being the group --OR₈ wherein R₈ is C₁ -C₃ alkyl; and(c) B and B' are each selected from the group consisting of:(i) phenyl,mono-substituted and di-substituted phenyl; (ii) the unsubstituted,mono-, and di-substituted heteroaromatic groups furanyl,benzofuran-2-yl, thienyl and benzothien-2-yl, each of said phenyl andheteroaromatic substituents in (c)(i) and (ii) being selected from thegroup consisting of hydroxy, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, aryl,indolino, fluoro and chloro; and (iii) the group represented by thefollowing graphic formula: ##STR27## wherein E is carbon and D isoxygen, R₁₂ is C₁ -C₃ alkyl or C₁ -C₃ alkoxy, R₁₃ and R₁₄ are eachhydrogen or C₁ -C₃ alkyl, and p is 0 or 1; or (iv) B and B' takentogether form fluoren-9-ylidene, adamantylidene, bornylidene,norbornylidene or bicyclo(3.3.1)nonan-9-ylidene.
 4. A photochromicarticle comprising a polymeric organic host material selected from thegroup consisting of poly(methyl methacrylate), poly(ethylene glycolbismethacrylate), poly(ethoxylated bisphenol A dimethacrylate),thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral,polyurethane and polymers of members of the group consisting ofdiethylene glycol bis(allyl carbonate) monomers, diethylene glycoldimethacrylate monomers, ethoxylated phenol bismethacrylate monomers,diisopropenyl benzene monomers and ethoxylated trimethylol propanetriacrylate monomers and a photochromic amount of the compound of claim3.
 5. A photochromic composition comprising a coating composition and aphotochromic amount of the compound of claim
 3. 6. The photochromiccomposition of claim 5 wherein said compound is water soluble.
 7. Thephotochromic composition of claim 6 wherein the water solubility of saidcompound is at least one gram per liter.
 8. A photochromic articlecomprising a polymeric organic host material and a photochromic amountof the compound of claim
 1. 9. The photochromic article of claim 8wherein the polymeric organic host material is selected from the groupconsisting of poly(C₁ -C₁₂ alkyl methacrylates), poly(oxyalkylenedimethacrylates), poly(alkoxylated phenol methacrylates), celluloseacetate, cellulose triacetate, cellulose acetate propionate, celluloseacetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinylchloride), poly(vinylidene chloride), thermoplastic polycarbonates,polyesters, polyurethanes, poly(ethylene terephthalate), polystyrene,poly(alpha methylstyrene), copoly(styrene-methylmethacrylate),copoly(styrene-acrylonitrile), polyvinylbutyral and polymers of membersof the group consisting of bis(allyl carbonate) monomers, polyfunctionalacrylate monomers, polyfunctional methacrylate monomers, diethyleneglycol dimethacrylate monomers, diisopropenyl benzene monomers,ethoxylated bisphenol A dimethacrylate monomers, ethylene glycolbismethacrylate monomers, poly(ethylene glycol) bismethacrylatemonomers, ethoxylated phenol bismethacrylate monomers, alkoxylatedpolyhydric alcohol acrylate monomers, styrene monomers, urethaneacrylate monomers, glycidyl acrylate monomers, glycidyl methacrylatemonomers and diallylidene pentaerythritol monomers.
 10. The photochromicarticle of claim 9 wherein the polymeric organic host material is asolid transparent polymer selected from the group consisting ofpoly(methyl methacrylate), poly(ethylene glycol bismethacrylate),poly(ethoxylated bisphenol A dimethacrylate), thermoplasticpolycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane andpolymers of members of the group consisting of diethylene glycolbis(allyl carbonate) monomers, diethylene glycol dimethacrylatemonomers, ethoxylated phenol bismethacrylate monomers, diisopropenylbenzene monomers and ethoxylated trimethylol propane triacrylatemonomers.
 11. The photochromic article of claim 10 wherein thephotochromic compound is present in an amount of from 0.05 to 1.0milligram per square centimeter of organic host material surface towhich the photochromic substance(s) is incorporated or applied.
 12. Thephotochromic article of claim 11 wherein said transparent polymer is anoptical element.
 13. The photochromic article of claim 12 wherein saidoptical element is a lens.
 14. A photochromic composition comprising acoating composition and a photochromic amount of the compound ofclaim
 1. 15. The photochromic composition of claim 14 wherein saidcompound is water soluble.
 16. The photochromic composition of claim 15wherein the water solubility of said compound is at least about one gramper liter.
 17. The photochromic composition of claim 14 wherein thecoating composition is chemically compatible with said compound and issubstantially free of ultraviolet light absorbing materials in amountsthat interfere with the activation of said compound.
 18. A compoundselected from the group consisting of:(a)2,2-bis(4-methoxyphenyl)-5-methoxycarbonyl-6-bis(3-dimethylaminopropyl)amino-2H-naphtho1,2-b!pyran; (b)2,2-diphenyl-5-methoxycarbonyl-6-(3-dimethylaminopropyl)methylamino-2H-naphtho1,2-b!pyran; (c)2,2-diphenyl-5-methylol-6-(3-dimethylaminopropyl)methylamino-2H-naphtho1,2-b!pyran; (d) 3,3-bis(4-methoxyphenol)-8-bis(3-dimethylaminopropyl)amino-3H-naphtho 2,1-b!pyran; (e)3,3-diphenyl-8-(3-dimethylaminopropyl)-methylamino-3H-naphtho2,1-b!pyran; and (f)2,2-diphenyl-5-methoxycarbonyl-6-bis(3-dimethylaminopropyl)amino-2H-benzopyran.19. A compound comprising a quaternary ammonium salt of the compound ofclaim
 18. 20. A photochromic article comprising a polymeric oganic hostmaterial selected from the group consisting of poly(methylmethacrylate), poly(ethylene glycol bismethacrylate), poly(ethoxylatedbisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinylacetate), polyvinylbutyral, polyurethane and polymers of members of thegroup consisting of diethylene glycol bis(allyl carbonate) monomers,diethylene glycol dimethacrylate monomers, ethoxylated phenolbismethacrylate monomers, diisopropenyl benzene monomers and ethoxylatedtrimethylol propane triacrylate monomers, and a photochromic amount ofthe compound of claim 19.